2-Nitro-9,10-dihydro-9,10-ethenoanthracene | 17604-37-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 2-Nitro-9,10-dihydro-9,10-ethenoanthracene
• 英文别名: 2-nitrodibenzobicyclo<2.2.2>octatriene；2-Nitro-9,10-aetheno-9,10-dihydro-anthracen；4-Nitrotetracyclo[6.6.2.02,7.09,14]hexadeca-2(7),3,5,9,11,13,15-heptaene
• CAS: 17604-37-4
• 化学式: C₁₆H₁₁NO₂
• 分子量: 249.269
• InChiKey: TXYPCTJSTVGXTG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-Nitro-9,10-dihydro-9,10-ethenoanthracene 在 盐酸 、 硫酸 、 铁粉 、 sodium nitrite 作用下， 以 乙醇 为溶剂， 反应 1.75h， 生成 2-Hydroxydibenzobicyclo<2.2.2>octatriene
  参考文献：
  名称：

  Distortion of Olefin and Carbonyl .pi.-Orbitals in Dibenzobicyclo[2.2.2]octatrienes and Dibenzobicyclo[2.2.2]octadienones. Unsymmetrization of .pi. Lobes Arising from .pi.-.pi. Orbital Interactions

  摘要：

  We have detected the unsymmetrical pi faces of the olefin group in 2-substituted dibenzobicyclo-[2.2.2]octatrienes (2-substituted 9,10-dihydro-9,10-ethenoanthracenes) and the carbonyl groups of 2-substituted and 3-substituted dibenzobicycla[2.2.2]octadienones (2-substituted and 3-substituted 9,10-dihydro-9,10-(11-ketoethano)anthracenes), wherein alpha-type overlaps of the pi orbitals are involved, in a similar manner to longicyclic conjugation. An intrinsically nonequivalent substituent at distal positions modulates the epoxidation and dihydroxylation of the olefin group and the reduction of the carbonyl group. Both systems exhibit similar substituent effects: an ''electron-withdrawing'' substituent such as a nitro or fluoro group gave a large to moderate bias (preferred syn attack with respect to the substituent) whereas an ''electron-donating'' methoxy substituent exhibited a negligible bias. Herein we interpret these biases or nonbiases in terms of unsymmetrization of pi lobes of the olefin and carbonyl pi orbitals, arising from nonequivalent pi-pi interactions rather than from an electron-donating or -withdrawing effect.

  DOI：

  10.1021/jo00093a032
• 作为产物：
  描述：

  dimethyl 9,10-dihydro-9,10-ethenoanthracene-11,12-dicarboxylate 在 sodium hydroxide 、 硝酸 、 乙酸酐 、 铜 作用下， 以 喹啉 、 甲醇 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 2-Nitro-9,10-dihydro-9,10-ethenoanthracene
  参考文献：
  名称：

  Distortion of Olefin and Carbonyl .pi.-Orbitals in Dibenzobicyclo[2.2.2]octatrienes and Dibenzobicyclo[2.2.2]octadienones. Unsymmetrization of .pi. Lobes Arising from .pi.-.pi. Orbital Interactions

  摘要：

  We have detected the unsymmetrical pi faces of the olefin group in 2-substituted dibenzobicyclo-[2.2.2]octatrienes (2-substituted 9,10-dihydro-9,10-ethenoanthracenes) and the carbonyl groups of 2-substituted and 3-substituted dibenzobicycla[2.2.2]octadienones (2-substituted and 3-substituted 9,10-dihydro-9,10-(11-ketoethano)anthracenes), wherein alpha-type overlaps of the pi orbitals are involved, in a similar manner to longicyclic conjugation. An intrinsically nonequivalent substituent at distal positions modulates the epoxidation and dihydroxylation of the olefin group and the reduction of the carbonyl group. Both systems exhibit similar substituent effects: an ''electron-withdrawing'' substituent such as a nitro or fluoro group gave a large to moderate bias (preferred syn attack with respect to the substituent) whereas an ''electron-donating'' methoxy substituent exhibited a negligible bias. Herein we interpret these biases or nonbiases in terms of unsymmetrization of pi lobes of the olefin and carbonyl pi orbitals, arising from nonequivalent pi-pi interactions rather than from an electron-donating or -withdrawing effect.

  DOI：

  10.1021/jo00093a032

文献信息

• Orbital distortion in dibenzobicyclo(2.2.2)octatrienes. Biased epoxidation and dihydroxylation of the olefin moiety.
  作者：Naoki HAGA、Tomohiko OHWADA、Iwao OKAMOTO、Koichi SHUDO

  DOI：10.1248/cpb.40.3349

  日期：——

  Epoxidation and dihydroxylation of the olefin moiety of 2-substituted dibenzobicyclo[2.2.2] octatrienes were investigated. These reactions exhibited substituent effect : 2-nitodibenzo bicyclo[2.2.2]octatriene gave predominantly the syn-epoxide and the syn-diol, with a diastereomeric excess of 54% to 76%. respectively. On the other hand, the 2-methoxy substrate showed only a small preference in the reactions, giving a slight excess of the antiproducts. This effect can be interpreted in terms of the perturbation of the occupied π orbital of the ethylene moiety arising from the mixing of the π orbitals (in particular, the HOMO) of convex-substituted dihydroxyanthracene, wherein the σ type overlaps are involved in a manner similar to the longicyclic conjugation.

  对2-取代二苯并双环[2.2.2]辛三烯的烯烃部分进行了环氧化和二羟基化研究。这些反应表现出取代效应：2-硝基二苯并双环[2.2.2]辛三烯主要生成顺式环氧化物和顺式二醇，非对映异构体过剩率分别为54%和76%。另一方面，2-甲氧基底物在反应中仅表现出轻微的偏好，生成少量反产物。这种效应可以用乙烯部分被占π轨道的扰动来解释，这种扰动是由凸取代二羟基蒽的π轨道（特别是HOMO）的混合引起的，其中σ型重叠以类似于长环共轭的方式参与。
• Distortion of Olefin and Carbonyl .pi.-Orbitals in Dibenzobicyclo[2.2.2]octatrienes and Dibenzobicyclo[2.2.2]octadienones. Unsymmetrization of .pi. Lobes Arising from .pi.-.pi. Orbital Interactions
  作者：Tomohiko Ohwada、Iwao Okamoto、Naoki Haga、Koichi Shudo

  DOI：10.1021/jo00093a032

  日期：1994.7

  We have detected the unsymmetrical pi faces of the olefin group in 2-substituted dibenzobicyclo-[2.2.2]octatrienes (2-substituted 9,10-dihydro-9,10-ethenoanthracenes) and the carbonyl groups of 2-substituted and 3-substituted dibenzobicycla[2.2.2]octadienones (2-substituted and 3-substituted 9,10-dihydro-9,10-(11-ketoethano)anthracenes), wherein alpha-type overlaps of the pi orbitals are involved, in a similar manner to longicyclic conjugation. An intrinsically nonequivalent substituent at distal positions modulates the epoxidation and dihydroxylation of the olefin group and the reduction of the carbonyl group. Both systems exhibit similar substituent effects: an ''electron-withdrawing'' substituent such as a nitro or fluoro group gave a large to moderate bias (preferred syn attack with respect to the substituent) whereas an ''electron-donating'' methoxy substituent exhibited a negligible bias. Herein we interpret these biases or nonbiases in terms of unsymmetrization of pi lobes of the olefin and carbonyl pi orbitals, arising from nonequivalent pi-pi interactions rather than from an electron-donating or -withdrawing effect.